摘要
以壳聚糖为原料,采用一步水热碳化和磺化法合成壳聚糖基固体酸材料(CASA),并将其用于催化无溶剂条件下果糖脱水合成5-羟甲基糠醛(5-HMF),考察了催化剂用量、反应温度、反应时间及催化剂循环利用次数对脱水反应的影响,并与甲壳素基固体酸材料(CISA)进行了催化性能比较。采用X射线衍射、扫描电镜、吡啶吸附红外光谱对CASA材料进行了结构和酸性质表征,建立了催化剂结构与性能的关系。结果表明,CASA材料含有大量的表面强Br?nsted酸性位点,因而其催化性能较CISA突出;当m(果糖)∶m(CASA)=6∶1、120℃反应5 h时,5-HMF的收率高达63.2%,且CASA可重复利用4次而无明显失活。
A kind of chitosan-derived solid acid(CASA) material was successfully synthesized via in situ partially hydrothermal carbonization followed by sulfonation with chitosan as raw materials. Subsequently,the CASA material was used for catalytic fructose dehydration to 5-hydroxymethylfurfural(5-HMF) under solvent-free conditions. The effects of catalyst amount, reaction temperature, reaction time and catalyst recyclability on the dehydration were studied in detail. Meanwhile, its catalytic activity was compared with that of chitin-derived solid acid(CISA) material. The obtained CASA material was characterized by various techniques, such as X-ray diffraction, scanning electron microscopy and infrared spectra of pyridine adsorption. A relationship between the catalyst structure and properties was established. The results suggested that there were a lot of strong Br?nsted acid sites on the CASA surface. Therefore, its catalytic performance was more outstanding than that of CISA. The 5-HMF yield was up to 63.2% at 120 ℃ within 5 h when the mass ratio of fructose to CASA material was 6∶1. Moreover, the CASA catalyst could be recycled up to 4 times without any obvious deactivation.
引文
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